MODULE 1

Electrical Conductivity in metals

Free electron concept
All metal atoms consist of valence electrons which are responsible for electrical conduction.
Valence electrons are loosely bound to the nucleus. When a large number of atoms join to form a
metal, the boundaries of the neighbouring atoms overlap, and thus, valence electrons can move
easily throughout the body of the metal.

These electrons are called free electrons or conduction electrons which account for properties
such as electrical conductivity, thermal conductivity, opacity, surface luster etc.
Classical free electron theory
This theory was developed by Drude and Lorentz and hence is also known as Drude-Lorentz
theory.
According to this theory, a metal consists of electrons which are free to move about in the body
of the metal like molecules of a gas in a container. The velocity distribution of the electrons
obeyed the Maxwell-Boltzmann law. The Drude-Lorentz theory could successfully explain the
Ohm’s law and the high electrical conductivity in metals.
Assumptions
1. A metal is imagined as a structure of 3-dimensional array of ions between which, there are
freely moving valence electrons (conduction electrons) confined to the body of the material.
2. Mutual repulsion between electrons is ignored and hence potential energy is taken as zero.
Therefore the total energy of the electron is equal to its kinetic energy.
3. The free electrons are treated as equivalent to gas molecules and thus they are assumed to
obey the laws of kinetic theory of gases. In the absence of field, the energy associated with each
3
electron at a temperature T is given by kT
2
where k =1.38 × 10-23 J/K.

Drude Hendrik Lorentz

4. If no electric field is applied on a conductor, the free electrons move in random directions.
They collide with each other and also with the positive ions. Since the motion is completely
random, average velocity in any direction is zero. If a constant electric field is established inside
a conductor, the electrons experience a force F = -eE due to which they move in the direction
opposite to direction of the field. These electrons undergo frequent collisions with positive ions.
In each such collision, direction of motion of electrons undergoes random changes. As a result,
in addition to the random motion, the electrons are subjected to a very slow directional motion.
This motion is called drift and the average velocity of this motion is called drift velocity (V d).
Thermal velocity
The ionic cores will be vibrating constantly about a mean position due to thermal agitation. The
thermal agitation also causes the conduction electrons to keep moving constantly inside the
metal. The velocity with which the free electrons keep moving due to thermal agitation is called
thermal velocity.
Mean collision time and mean free path
Mean collision time (τ) is the average time that elapses between two consecutive collisions of an
electron with lattice ions.
Average distance traveled by the conduction electrons between successive collisions is called
mean free path (λ).
If ‘v’ is the total velocity (combined effect of thermal and drift velocities) of an electron, then
mean free path, λ= v τ
Relaxation time (τr)
When the field E is withdrawn, due to the collision of the electrons with lattice ions and lattice
defects, their velocity will start to decrease. This process is called relaxation.
1
The relaxation time (τr) is the time required for the drift velocity to reduce to of its initial
e
value, when the electric field is turned off.
If the probability of scattering of electrons by lattice ions is same in all directions, mean collision
time can be treated as relaxation time. Its value is of the order of 10-14s.
Mobility
Mobility of a charge carrier is the ratio of the drift velocity to the electric field.
Vd
Mobility μ =
E
where ‘Vd’ is the drift velocity and E is the applied electric field.
2
m
The unit of mobility is .
Volt .. Sec
The mobility represents the ease with which electrons move in a solid.
Expression for drift velocity
Consider a conductor subjected to an electric field E in the x-direction.
The force on the electron due to the electric field = eE.
In the steady state, let ‘Vd’ be the drift velocity and ‘τ’ the mean collision time.
 Vd
By Newton’s law, eE = ma = m
τ
eEτ
Vd = --------------- (1)
m
Expression for electrical conductivity in metals
Consider a wire of area of cross section ‘A’ subjected to an electric field E.
If ‘n’ is the concentration of the electrons, ‘e’ charge on an electron, ‘V d’ drift velocity, Current
flowing through the wire is given by,
I = neAVd

I
But Current density J = = neVd --------------- (2)
A
By Ohm’s law, J = σ E
J
Thus electrical conductivity σ = -------------- (3)
E
Substituting the value of J from equation (2) in equation (3),
Vd
σ = ne = neμ------------- (4)
E
Substituting the value of V d from equation (1),
 2
ne τ
σ= ------------- (5)
m

Effect of temperature and impurity on electrical resistivity of metals (Matthiessen’s rule)

The variation of electrical resistivity (ρ) with temperature T for a metal is shown below:

Resistivity arises due to scattering of conduction electrons. In metals, two types of scattering
mechanisms exist.
1. Resistivity ρphdue to scattering of electrons by lattice vibrations (phonons) which is
temperature dependent and is called ideal resistivity.
2. Resistivity ρi due to the scattering of the electrons by the presence of impurities and
imperfections. This resistivity is temperature independent and exists even at 0K. Hence it is
called residual resistivity.
The total resistivity ρ of a material is given by,
ρ = ρph+ ρi
This is called Matthiessen’s rule. Matthiessen’s rule states that the total resistivity of a metal is
the sum of the resistivity due to phonon scattering (temperature dependent) and the resistivity
due to scattering by impurities (temperature independent).
At low temperatures, lattice vibration is negligible and phonon scattering is very less.
∴At low temperatures, ρ ≈ ρi
At high temperatures, lattice vibration becomes very significant and resistivity becomes linearly
dependent on temperature.
∴At high temperatures, ρ ≈ ρph
Hall Effect
The Hall-effect principle is named for physicist Edwin Herbert Hall. Hall-effect results from the
interaction of charged particles, like electrons, in response to electric and magnetic fields.
Consider a rectangular slab that carries a current I in the X-direction. A uniform magnetic field
of flux density B is applied along the Z-direction. The current carriers experience a force
(Lorentz force) in the downward direction. This leads to an accumulation of electrons in the
lower face of the slab. This makes the lower face negative. Similarly the deficiency of electrons
makes the upper face positive. As a result, an electric field is developed along Y-axis. This effect
is called Hall Effect and the emf thus developed is called Hall voltage V H. The electric field
developed is called Hall field EH.

In metals, the Hall voltages are generally negative, indicating that the electric current is
composed of moving negative charges, or electrons. The Hall voltage is positive, however, for a
few metals such as beryllium, zinc, and cadmium, indicating that these metals conduct electric
currents by the movement of positively charged carriers called holes. In semiconductors, in
which the current consists of a movement of positive holes in one direction and electrons in the
opposite direction, the sign of the Hall voltage shows which type of charge carrier predominates.
 Edwin Herbert Hall
Importance of Hall effect
Hall effect proved that band theory of solids is more accurate than free electron theory. Hall
effect proved that electrons are the majority carriers in all the metals and n-type semiconductors.
In p-type semiconductors, holes are the majority carriers.
Applications of Hall effect
1. To determine the type ( n-type or p-type) of semiconductors.
2. To determine the concentration of the carriers.
3. In nondestructive testing.
4. In Hall generators.
Wiedemann-Franz law
This law is named after Gustav Wiedemann and Rudolph Franz.Thermal Conductivity (K)is the
degree (measure) of capacity of a material to conduct heat. Electrical Conductivity (σ)is the
degree (measure) of capacity of a material to conduct electricity.
 Gustav Wiedemann

According to Wiedemann-Franz law, the ratio of thermal conductivity to electrical conductivity

of a metal is directly proportional to absolute temperature.
K
i.e, ∞T
σ
K
Or, = L, a constant for all temperatures and is known as Lorentz number.
σT
3 kB 2
L= [ ]
2 e

=1.12×10-8 WΩ K-2
Failure of classical free electron theory
1. Temperature dependence of electrical resistivity
1 3
According to kinetic theory of gases, Kinetic energy of electron, mv2 = kT
2 2

∴v=
√ 3 kT
m
or v ∞ √ T
2
ne τ
But electrical conductivity σ = and
m
mean free path, λ= v τ,
 2
ne λ
∴σ=
mv
1
Since v ∞ √ T , σ ∞
√T
or resistivity, ρ∞ √ T

But experimental observation is ρ ∞ T.

Thus in this case, classical free electron theory is not agreeing with the experimental
observations.
2. Specific heat
Specific heat, Cv is the amount of heat required to change the heat content of exactly 1 gram of a
material by exactly 1°C.
3
The theoretically predicted value of specific heat (Cv = R) of a metal does not agree with the
2
experimentally obtained value (10-4 RT).
Experimentally observed value of specific heat is far lower than expected value.
3. Dependence of electrical conductivity on electron concentration
As per the classical free electron theory,
2
ne τ
σ=
m
Or, σ ∞ n
But experimental observation disagrees with this.
4. Positive Hall co-efficient of Zinc
Metals are expected to exhibit negative Hall co-efficient since current carriers in them are
electrons. The free electron theory cannot explain why Zinc and some other metals have positive
Hall co-efficient.
5. Wiedemann-Franz law
According to Wiedemann-Franz, the ratio of thermal conductivity to electrical conductivity of a
metal is directly proportional to absolute temperature.
K
i.e, = L=1.12×10-8 WΩ K-2 a constant for all temperatures.
σT
But experimentally calculated value does not match with this value.
6. The free electron theory cannot explain the classification of materials into conductors,
semiconductors and insulators.
7. This theory fails to explain ferromagnetism, superconductivity, photoelectric effect, Compton
effect and blackbody radiation.
Quantum free electron theory

Arnold Johannes Wilhelm Sommerfeld

Classical free electron theory could not explain many physical properties. In classical free
electron theory, we use Maxwell-Boltzmann statistics which permits all the free electrons to gain
energy. In 1928, Arnold Johannes Wilhelm Sommerfeld developed a new theory, in which he
retained some of the features of classical free electron theory and included quantum mechanical
concepts and Fermi-Dirac statistics to the free electrons in the metal. This theory is called
quantum free electron theory. Quantum free electron theory permits only a fraction of electrons
to gain energy. The main assumptions of this theory are:
1. The electrons move in a constant potential inside the metal and are confined within defined
boundaries.
2. The attraction between the electrons and the lattice ions and the repulsion between the
electrons themselves are ignored.
3. The energy values of conduction electrons are quantized and are realized in terms of a set of
energy levels.
4. The distribution of electrons in various allowed energy levels takes place according to Pauli’s
exclusion principle.
Fermi-Dirac statistics
According to Fermi-Dirac statistics, the probability that an electron occupies an energy level E at
thermal equilibrium is given by,
 1
f(E) = ( E −EF
)
1+ e kT
where EF is called Fermi level,. Fermi level is the highest filled energy level by an electron at 0
K.
Energy corresponding to Fermi level is known as Fermi energy. Fermi energy is the maximum
energy that a free electron can have in a conductor at 0K.
The probability f(E) is known as Fermi factor.
Fermi Velocity (vF)
The velocity of the electrons occupying the Fermi level is called Fermi velocity (v F).
1
EF = mvF2
2

Or,vF =
√ 2 EF
m
where m is the mass of the electron and EF is the Fermi energy.
Fermi Temperature (TF)
Fermi Temperature is the temperature at which the average thermal energy of the free electron in
a solid becomes equal to the Fermi energy at 00K.
The thermal energy possessed by electrons is given by the product kTF, then kTF =EF
EF
or TF = where k is the Boltzmann constant and EF is the Fermi energy at 00K.
k
The Fermi temperature is only a theoretical concept, since at ordinary temperature, it is not
possible for the electrons to receive thermal energy in a magnitude of E F. For metals order of
Fermi energy is a few electron volts. If EF= 3 eV,
− 19
EF 3× 1.6 ×10
TF = = − 23 = 34783 K
k 1.38 ×10
This temperature is quite an exaggerated temperature to be realized in practice.
Effect of temperature on Fermi factor
Fermi factor is given by,
1
f(E) = ( E −EF
)
1+ e kT
where k is the Boltzmann constant and EF is the Fermi energy at 00K.
At T=0K, for E < EF, f(E)=1

At T=0K, for E >EF, f(E)=0

At T=0K, for E = EF, f(E)= indeterminate

At T>0K, for E=EF, f(E)= ½.

All these results are depicted in the figure.

Fermi energy at absolute zero (0K) temperature

2
ℎ 3n
EF (0) = ( ) ( ¿2/3
8m π
Expression for electrical resistivity/conductivity and its temperature dependence
According to Quantum free electron theory, electrical conductivity of a metal is given by,
2
ne τF
σ=
m
λ❑
Here τF= , where vF is the Fermi velocity which is the velocity of electrons occupying Fermi
vF
level and λ the mean free path.
 2
n e λ❑
Now electrical conductivity can be expressed as, σ = ---------(1)
m vF
Here vF is independent of temperature but λ is temperature dependent. As the temperature
increases, the lattice ions start vibrating with larger amplitudes and offer scattering of the
electrons which results in the reduction in the value of mean free path of the electrons.
1
i.e., λ ∞
T
1
But from equation (1), σ ∝ λ ∴σ ∝ and ρ ∞ T
T
Classical free electron theory and quantum free electron theory-Comparison
Similarities
1. Valence electrons travel in a constant potential inside the metal.
2. The mutual repulsion between the electrons and the force of attraction between the electrons
and ions are considered insignificant.
Differences
1. According to classical free electron theory, free electrons obey Maxwell-Boltzman statistics.
According to quantum free electron theory, free electrons obey Fermi-Dirac statistics.
2. According to classical free electron theory, free electrons can possess any energy values and it
is possible that many electrons possessing same energy. According to quantum free electron
theory, free electrons can occupy certain energy levels with discrete energy values and they obey
Pauli’s exclusion principle. Hence no two electrons possess same energy.
Merits of quantum free electron theory
Temperature dependence of electrical resistivity/conductivity
According to Quantum free electron theory, electrical conductivity of a metal is given by,
2
ne τF
σ=
m
λ❑
Here τF= , where vF is the Fermi velocity which is the velocity of electrons occupying Fermi
vF
level and λ the mean free path.
2
n e λ❑
Now electrical conductivity can be expressed as, σ = ---------(1)
m vF
Here vF is independent of temperature but λ is temperature dependent. As the temperature
increases, the lattice ions start vibrating with larger amplitudes and offer scattering of the
electrons which results in the reduction in the value of mean free path of the electrons.
 1
i.e., λ ∞
T
1
But from equation (1), σ ∝ λ ∴σ ∝ and ρ ∞ T
T
This result is in accordance with experimental observation.
2. Specific heat
3
According to classical free electron theory, specific heat C v = R. But experimentally observed
2
value is around 10-4 RT which is very low. According to classical free electron theory, all
electrons are capable of absorbing heat energy. Thus the theory predicts a large value of specific
heat. But according to quantum free electron theory, only those electrons which occupy energy
levels close to Fermi level E F absorb heat energy and hence specific heat value becomes very
small.
3. Thermionic emission
When a metal surface is heated it emits electrons. This is called thermionic emission. Here heat
provides enough energy for an electron to escape from the surface.
The number of electrons emitted per second from a substance is known as the rate of thermionic
emission. This value depends on the nature of the material, surface temperature and surface area.

−W
The emitted electron current density is given by, J = AT2e kT

where ‘T’ is the metal temperature in Kelvin, ‘e’ charge on an electron, ‘W’ the work function of
the metal, ‘k’ the Boltzman constant and ‘A = 1.2 × 106 Am-2 K-2’ is the Richardson constant.
This relation is called Richardson-Dushman equation which obeys well as per quantum free
electron theory.
Demerits of quantum free electron theory
1. It fails to explain properties of metal alloys.
2. It fails to explain why only some solids are metals and others are either semiconductors or
insulators.
Solved Problems
1. Calculate the mobility of electrons in copper assuming that each atom contributes one free
electron for conduction. Given: Resistivity of copper = 1.7×10 -8Ohm-m, Atomic weight = 63.54,
Density = 8.96×103kg/m3 and Avogadro’s number NA = 6.025×1026/K mole.
Solution:
Valency × N A × D
n=
Atomic weigℎt
 26 3
1× 6.025× 10 × 8.96 ×10
=
63.54

= 8.5×1028 m-3

σ = neμ

σ
⸫μ=
ne

1
=
ρne
1
= −8 28 − 19
1.7 ×10 × 8.5× 10 × 1.6 ×10

= 4.325×10-3 m2/vs

2. The Fermi level in the silver is 5.5 eV. Find the velocity of conduction electrons in silver.
Solution:
1
EF = mvF2
2

⸫ vF =
√ 2 EF
m

√
−19
2 ×5.5 × 1.6× 10
= −31
9.11×10

= 1.39×106m/s

3. Calculate the probability of an electron occupying an energy level 0.01 eV above the Fermi
level at 100 K in a material.
Solution:
1
f(E) =
( E −E

1+ e kT
) F
 1
=
( ) = 0.239
−19
0.01 ×1 , 6 ×10
−23
1.38 ×10 × 100
1+ e

Objective questions
1. In a metal, if the temperature is increased, then resistivity
A) Increases B) Decreases C) Remains same D) None of these
2. For T > 0K, probability of occupancy of Fermi level is
A) 75% B) 90% C) 100% D) 50%
3. The electron mobility in metals is given by
A) vd/V B) vd/E C) vd/L D) vd/τ
4. The Fermi factor for E = EF at any temperature is
A) 1 B) ½ C) 0 D) 2
5. If the mobility of electron in a metal increases, the resistivity
A) Decreases B) Increases
C) Remains constant D) None of these.
6. Ohms law relates to the electric field E, conductivity σ and current density J as
A) J = E/σ B) J = σE2 C) J = σ/E D) J = σE
7. The average drift velocity v d of electrons in a metal is related to the electric field and collision
time τ as

A)
√ eEτ
m
B) m
√ eEτ
C)
eEτ
m
D)
m
eEτ

8. Experimentally specific heat at constant volume Cv is given by

A) 3/2 R B) 10 -4 RT C) 2/3 R D) 10 -4 R
9. If the mobility of the electron is 7 × 10 -3 m2/vs, when accelerated by a field 1v/cm, the v d is
given by
A) 7 × 10-3 m/s B) 0.7 m/s C) 7 × 10 -2 m/s D) 0.007 m/s
10. The temperature dependence for electrical resistivity of metal is
A) ρ ∞ 1/T B) ρ ∞ 1/√T C) ρ∞√T D) ρ∞ T
11. According to quantum free electron theory, the energy levels in a metal are
A) Continuous B) Discrete C) Overlapping D) None
12. Which one of the following is correct expression for current density?
A) J = neAvd B) J = neA/vd C) J = nevd D) J = 1/nevd
13. The value of Fermi distribution function at absolute zero (T= 0 K) is 1, under the condition
A) E = EF B) E > EF C) E >> EF D) E < EF
14. If the Fermi energy of silver is 5.5 eV, the Fermi velocity of conduction electron is
A) 0.98 × 106 m/s B) 1.39 × 106 m/s C) 2.46 × 105 m/s D) None of these
15. The collision time and root mean square velocity of an electron at room temperature are
3×10-14 sec and 1×105 m/s respectively. The classical value of mean free path of the electron is
A) 3×10-19 nm B) 3Å C) 3 nm D) 17.3 nm
16. The quantum mechanical expression for electrical conductivity is
A) σ = m*vF/ne2λF B) σ = ne2λF/m2vF C) σ = m*vF/n2e2λF D) σ = m*/ne2λF
17. Mobility of electron is
A) Reciprocal of conductivity B) Flow of electrons per unit
C) Reciprocal of resistivity D) Average electron drift velocity per unit electric field
18. The classical value of molar specific heat of a conductor is
A) 3/2 R B) ½ R C) 3R D) 5/2 R
19. Classical free electron theory was developed by
A) Drude and Lorentz B) Fermi and Dirac
C) Bose and Einstein D) Sommerfel
20. Average distance traveled by the conduction electrons between successive collisions is called
A) Interplanar distance B) Wavelength C) Mean free path D) Relaxation

Important Questions
1. Define drift velocity, mobility and relaxation time for free electron, derive the expression for
conductivity in metals.
2. Write down the assumptions of classical free electron theory.
3. Derive an expression for electrical conductivity in metals.
4. Explain failure of classical free electron theory.
5. Explain Matthiessen’s rule.
6. Explain Hall effect.
7. Write a note on Wiedemann-Franz law.
8. Discuss the various drawbacks of classical free electron theory of metals. What are the
assumptions made in quantum theory to overcome the same?
9. What is Fermi energy? Discuss variation of Fermi factor with energy and temperature.
10. Write a note on merits of quantum free electron theory.

Problems
1. A uniform silver wire has resistivity 1.54×10 -8 ohm-m at room temperature for an electric field
2 v/m. Calculate relaxation time and drift velocity of the electrons, assuming that there are
5.8×1022 conduction electrons per cm3 of the material.
2. Calculate the drift velocity and thermal energy of electrons in a metal of thickness 1 mm
across which a potential of 1 volt is applied at temperature 300 K. Given the mobility of
electrons is 40 cm2/volt.sec.
3. Calculate the drift velocity and thermal energy of conduction electrons in copper at a
temperature of 300K, when a copper wire of length 2 m and resistance 0.02 Ω carries a current of
15 A. The mobility of free electrons in copper is 0.043 m2v-1s-1.
4. Calculate the conductivity of sodium given τ m= 2x10-14s. Density of sodium is 971 kg/m3, its
atomic weight is 23 and has one conduction electron/atom.
5. Obtain electron concentration, mobility and drift velocity in a metal for the following data:
Length = 5 m, Resistivity = 2.7 ×10-8 ohm-m, R = 6×10-2 ohm, I = 15 Amp,
Atomic weight = 26.98×10-3 kg/mol, Valency = 3, Density = 2.7×103 kg/m3.
6. Calculate the Fermi velocity and mean free path for conduction electrons in silver, given that
its Fermi energy is 5.5eV and relaxation time for electrons is 3.83x10-14s.
7. Calculate the probability of an electron occupying an energy level 0.02 eV above the Fermi
level at 200 K, in a material.
8. Calculate the probability of an electron occupying an energy level 0.02 eV above the Fermi
level and 0.02 eV below the Fermi level at 200 K.
9. Calculate the probability of an electron occupying an energy level 0.02 eV above the Fermi
level at 200 K and 400 k in a material.
10. The Fermi level in Silver is 5.5 eV. What are the energies for which the probabilities of
occupancy at 300K are 0.99 and 0.01?
11. The Fermi level in Potassium is 2.1eV. What are the energies for which the probabilities of
occupancy at 300K are 0.99 and 0.5?
12. Find the temperature at which there is 1 % probability that a state with energy 0.5eV above
Fermi energy will be occupied.